CN101547865B - Method for the production of titanium dioxide by oxygenating titanium tetrachloride - Google Patents
Method for the production of titanium dioxide by oxygenating titanium tetrachloride Download PDFInfo
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- CN101547865B CN101547865B CN200780044640.0A CN200780044640A CN101547865B CN 101547865 B CN101547865 B CN 101547865B CN 200780044640 A CN200780044640 A CN 200780044640A CN 101547865 B CN101547865 B CN 101547865B
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- titanium tetrachloride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/07—Producing by vapour phase processes, e.g. halide oxidation
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Abstract
The invention relates to the production of titanium dioxide by oxygenating titanium tetrachloride and then cooling the titanium dioxide particle-gas mixture while adding scouring particles in a cooling section, the gas-particle flow being made to rotate. According to the invention, the titanium tetrachloride is introduced into the axial oxygen-containing flow on the cross-sectional plane of the tubular reactor, but not in the radial direction. The flow velocity of the oxygen-containing gas exceeds 20 m/s, particularly reaching at least 40 m/s. The method according to the invention makes it possible to effectively remove accumulated TiO2 from the internal wall and the cooling section of the tubular reactor, thus increasing the cooling performance, and produce a TiO2 pigment which has a narrow grain size distribution.
Description
Technical field
The present invention relates to the oxidizing reaction by titanium tetrachloride and subsequently titanium dioxide granule-gaseous mixture is cooled off in cooling section prepare titanium dioxide, described gas-particle-stream is in the rotation.
Background technology
The method for preparing titanium dioxide-pigment of commercial use, i.e. so-called chlorination process is based on titanium tetrachloride (TiCl
4) with in tubular reactor, react generation titanium dioxide and chlorine through the oxidizing gas of preheating such as oxygen, air etc. and with specific additive.Oxidizing reaction is strong heat release, surpasses 1500 ℃ temperature so that reaction mixture has after complete reaction.With formed TiO
2-granules of pigments is cooled to be lower than about 400 ℃ and separate in following closely reactor cooling section from air-flow.The cooling that directly forms after finishing at particle must be carried out fast, in order to prevent further particle growth.Begin from here tubular reactor or reactor cooling section from the outside water cooling for this reason.
Yet the heat exchange in water coolant is because TiO
2-granules of pigments gathering and seriously hindered on tubular reactor inwall or reactor cooling section inwall.For this reason, according to US2,721,626 with decontamination particle (scouring solid) introducing reactor cooling section, and it should remove the pigment that accumulates in inwall.As cleaning solid, in this patent, use abrasive particle as having the gathering TiO of about granularity of 0.15 to 6.35mm
2-particle or quartz sand.With the one or more some input TiOs of described scouring solid in the reactor cooling section
2In-gas suspension the body.
At horizontal reactor-cooling section, because gravity, the decontamination particle just concentrates on pipe lower 1/3rd places in week in the short period of time after interpolation.During the pigment of adhesion was thoroughly removed in this zone of inwall, the upper zone cleaning cooling insufficient and the gas suspension body that is in pipe week was not enough.However in order to reach satisfied heat exchange, the dosage amount with the decontamination particle significantly improves usually.This has increased the weight of, and system is used for the preparation of decontamination particle, metering is added and the burden of separating, and especially produces thus to be used for the expensive of energy consumption and maintenance.
US 6,419, and 893B1 has described and effectively removed TiO on the reactor cooling section inwall
2-the method gathered.According to US 6,419,893B1 exists the burr that corkscrews as the drainage unit at inwall in the subregion of reactor cooling section at least, makes thus the flow overcooling section of decontamination particle to corkscrew.Described burr is arranged with 2-6 ° gradient.
US 2006/0133989A1 discloses reactor-cooling section that whole spirrillums make up, and should realize thus the inwall cleaning with the improvement of decontamination particle.
DE 1259851 discloses by the method for the reaction in the gas phase for the preparation of titanium dioxide, and wherein part gaseous reaction component tangential direction is introduced in the reactor.The method is designed to, and introduces reactive component by tangential direction on the one hand and reduces the formation of dirt settling on reactor wall and thoroughly mixed rapidly by producing anti-stream (so-called " eddy current ") realization response component on the other hand.Described eddy current namely broadens with flow direction to the cross circular section taper of reactor through this further enhancing.But eddy current causes the residence time of individual particle different lengths in reactor.
For the quality of titanium dioxide-pigment, particularly shinny ability (
) (tinting strength TS), narrow size-grade distribution is important.Yet not depend on reactive component fast thoroughly mixed but depend on TiO in order to produce narrow size-grade distribution
2Particle narrow residence time in reactor distributes, so that should avoid all kinds of anti-streams in reactor.
Goal of the invention
The object of the invention is to, the Innovative method that is different from prior art is provided, in order to make the inwall of tubular reactor and the inwall of reactor cooling section effectively break away from TiO by the decontamination particle on the one hand
2Gather and therefore realize the cooling efficiency of improvement, and make the TiO with narrow size-grade distribution on the other hand
2Pigment.
Described purpose is by reacting by titanium tetrachloride and the axial oxygen-containing gas of introducing in cylindrical tubular type reactor and cooling off the method realization for preparing titanium dioxide-particle with being about to particle, it is characterized in that, with titanium tetrachloride in the cross section of tubular reactor, but in the Off-Radial input tubular reactor, and the flow velocity of oxygen-containing gas particularly is at least 40m/s for surpassing 20m/s.
Other favourable embodiment of the present invention is described in the dependent claims.
Summary of the invention
The present invention illustrates by Fig. 1,2 and 3, but not therefore is intended to be limited.
The vertical section of reactor has been described in Fig. 1 diagram.Fig. 2 be for one embodiment of the invention along the viewgraph of cross-section of section 2-2 among Fig. 1 and Fig. 3 for for the viewgraph of cross-section of another embodiment of the invention along section 2-2 among Fig. 1.
This and hereinafter tubular reactor be that TiCl wherein occurs
4-oxidizing reaction and TiO
2-granuloplastic reactor part (referring to Fig. 1, numbering 10).Mean the and then part of tubular reactor as the reactor cooling section, wherein react by rapid cooling and stop and the gas suspension body is further cooled off.Usually be different from TiCl
4Additive and gas such as aluminum chloride, chlorine, nitrogen, basic salt etc. introduce in the reactor together.At this and " TiCl hereinafter
4" mean oxygen-free gas, mainly by TiCl
4The fluid that forms.At this and " O hereinafter
2" mean oxygen flow.
The present invention is set out by following cognition, the major portion of thermal output reactor-the cooling section section start carries out, TiO wherein
2The high temperature generation of-gas suspension body and the high-temperature drop of the driven nature of inside pipe wall.In this part, by decontamination grain flow or whole fluid are in the rotation, can significantly improve the rubbing effect of decontamination particle.By rotation and centrifugal force so that the decontamination particle distributing in whole pipe week and be pressed in simultaneously on the wall, thus with the evenly and thorough cleaning of wall.
About Fig. 1 to 3 with TiCl
4Preferably via in nozzle (12) input reactor (10).Nozzle means the ingress pipe of any type such as nozzle such as Venturi or the laval nozzle of passage, pipe etc. and any type within the scope of the invention.Reactor (10) has the cylindrical of the tool longitudinal axis (14).With oxygen in the longitudinal axis (14) input reactor (10).With TiCl
4Via nozzle (12) with in the tangential direction input reactor (10), but not radially.Fig. 2 has showed the cross section of reactor (10), and wherein radius marks with line (16).With TiCl
4To pass through in the tangential direction input reactor (10) of line (18) mark.Line (18) Off-Radial (16) is angle α approximately.
Nozzle (12) can be distributed near the position of line shaft reactor (10) around (Fig. 2).Also axial location each other of nozzle (12) alternately.
In another embodiment of the invention, also can be with TiCl
4Via in seam perforate (20) input reactor (Fig. 3).In this embodiment, the flow deflector (22) in seam perforate (20) causes the tangential direction of fluid, and described seam perforate (20) is arranged with corresponding angle α.
By in the titanium tetrachloride tangential direction ground input tubular reactor (10) that metering is added, whole fluid (reaction mixture and decontamination particle) is in the rotation according to the present invention in tubular reactor (10) and reactor cooling section.Because TiCl
4High specific gravity, it inputs significantly tangential pulse in fluid, this tangential pulse foot is to produce the rotation of long-term maintenance.
TiCl
4Mean in the tangential direction input tubular reactor (10), input is carried out in the cross section of tubular reactor (10), but with radially be the α＞0 ° angular range to＜90 °, preferred 1 ° to 15 ° and particularly 5 ° to 10 ° angular range carry out (Fig. 2 and 3).
Surprisingly, avoided anti-stream (eddy current) also to realize thus for all TiO at reactor (10) camber in the method for the present invention
2The uniform residence time of particle in reactor (10).Opposite with the instruction of DE 1259851, this is by following realization, axially the O of input
2-stream has that particularly the flow velocity of 40m/s and tubular reactor (10) have cylindrical at least above 20m/s.Can introduce high tangential pulse putting before this, in order to realize strong cleaning action, and not produce eddy current.(the TiCl that tangential direction is introduced
4) and the axial (O that introduces
2) ratio ratio of the product of proportion (flow velocity with) of specific impulse of reactive component is at least about 100.
When the decontamination particle is inputted in the situation of tubular reactor (10) high dispersing and caused thus the decontamination uniform particles to distribute and therefore evenly during the cleaning activity wall, for the cooling section wall, the improvement of heat exchange is by TiCl of the present invention at it
4-introduce and can further improve.Described dispersion can realize by the decontamination grain flow was in before input reactor in the violent rotation.This rotation can be for example by following realization, the similar cyclone separator of the jet pipe ground structure of namely preparing burden, and wherein the decontamination grain flow is introduced by pneumatic promotion tangential direction.
With according to US 6,419,893B1 compares with the method for US 2006/0133989A1, characteristics of the present invention are, make on the one hand whole fluid be in the rotation and therefore make the cleaning of inwall and the cooling optimization of gas suspensoid.In addition, along TiCl
4-inlet flow and the lower structural measure that expends of not needing are such as the helix structure of whole reactor cooling section or internal structure easy to wear.Compare in addition with according to the method for DE 1259851, characteristics of the present invention are, although TiCl
4The high tangential pulse of stream has avoided eddy current also can prepare the TiO of the shinny ability (TS) that has narrow size-grade distribution and therefore improve
2Granules of pigments.
Embodiment
Below illustrate for example the present invention, but not therefore be intended to be limited.
TiCl with 12t/h
4Input has in the tubular reactor of diameter of about 0.3m by the nozzle of 10 annulars, and makes it to react with oxygen-containing gas through preheating.Described nozzle in tubular reactor around settling near the position of line shaft and being evenly distributed on.All nozzles arrange in the tangential direction mode in cross section with identical direction, wherein the about 6 ° angle α of their Off-Radials.With this structure, the demand of decontamination particle is compared the simple radial array of nozzle be down to 1.2t/h by about 2.0.
Claims (11)
1. in cylindrical tubular type reactor, react and prepare with soon particle cooling the method for titanium dioxide granule by titanium tetrachloride and the oxygen-containing gas of axially introducing, it is characterized in that, with titanium tetrachloride in the cross section of tubular reactor, but in the described tubular reactor of Off-Radial ground input and the gas velocity of oxygen-containing gas for surpassing 20m/s.
2. according to claim 1 method is characterized in that, the gas velocity of oxygen-containing gas is 40m/s at least.
3. according to claim 1 method is characterized in that, with titanium tetrachloride with and radially be＞0 ° and＜angle α input between 90 °.
4. according to claim 3 method is characterized in that, with titanium tetrachloride with and radially be angle α input between 1 ° and 15 °.
5. according to claim 4 method is characterized in that, with titanium tetrachloride with and radially be angle α input between 5 ° and 10 °.
6. method one of according to claim 1-5 is characterized in that, with titanium tetrachloride by independent nozzle input.
7. according to claim 6 method is characterized in that, described nozzle axially arranges each other.
8. method one of according to claim 1-5 is characterized in that, by seam perforate input, described seam opening has the flow deflector that Off-Radial is arranged with titanium tetrachloride.
9. method one of according to claim 1-5 is characterized in that, the decontamination grain flow is introduced reactor.
10. according to claim 9 method is characterized in that, the decontamination grain flow is in the strong rotation before in input reactor.
11. method one of according to claim 1-5 is characterized in that TiCl
4The flow velocity of stream is compared O with the product of proportion
2The same product of stream is at least 100 times.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006060988 | 2006-12-20 | ||
| DE102006060988.3 | 2006-12-20 | ||
| DE102007048553.2 | 2007-10-09 | ||
| DE102007048553A DE102007048553A1 (en) | 2006-12-20 | 2007-10-09 | Process for the preparation of titanium dioxide by oxidation of titanium tetrachloride |
| PCT/EP2007/010780 WO2008077476A2 (en) | 2006-12-20 | 2007-12-11 | Method for the production of titanium dioxide by oxygenating titanium tetrachloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101547865A CN101547865A (en) | 2009-09-30 |
| CN101547865B true CN101547865B (en) | 2013-02-27 |
Family
ID=39431960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200780044640.0A Active CN101547865B (en) | 2006-12-20 | 2007-12-11 | Method for the production of titanium dioxide by oxygenating titanium tetrachloride |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP2129626B1 (en) |
| JP (1) | JP5409379B2 (en) |
| CN (1) | CN101547865B (en) |
| AU (1) | AU2007338499B2 (en) |
| DE (1) | DE102007048553A1 (en) |
| MX (1) | MX2009005234A (en) |
| RU (1) | RU2440297C2 (en) |
| SA (1) | SA110320025B1 (en) |
| TW (1) | TWI422527B (en) |
| WO (1) | WO2008077476A2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107720815A (en) * | 2017-11-14 | 2018-02-23 | 黄林海 | A kind of production method of rutile titanium dioxide |
| CN109704397A (en) * | 2019-02-15 | 2019-05-03 | 河南佰利联新材料有限公司 | A method of producing high durable semi-finished product titanium dioxide |
| WO2021212405A1 (en) * | 2020-04-23 | 2021-10-28 | 东华工程科技股份有限公司 | Chlorination process-based titanium dioxide oxidation reactor |
| CN112275247B (en) * | 2020-09-30 | 2022-05-24 | 河南佰利联新材料有限公司 | Combustion ring |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3306760A (en) * | 1964-01-04 | 1967-02-28 | Bayer Ag | Process for carrying out gas phase reactions |
| DE1259851B (en) * | 1965-04-15 | 1968-02-01 | Bayer Ag | Process for the production of inorganic, solid products by gas phase reaction |
| US3532462A (en) * | 1963-04-27 | 1970-10-06 | Bayer Ag | Method of effecting gas-phase reactions |
| US3663283A (en) * | 1969-10-02 | 1972-05-16 | Richard A Hebert | Process and apparatus for the production of finely-divided metal oxides |
| US3725526A (en) * | 1969-08-20 | 1973-04-03 | Montedison Spa | Process for producing pigment quality titanium dioxide |
| US20020155059A1 (en) * | 2001-04-24 | 2002-10-24 | Tekna Plasma Systems Inc. | Plasma synthesis of titanium dioxide nanopowder and powder doping and surface modification process |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03252315A (en) * | 1990-02-27 | 1991-11-11 | Osaka Titanium Co Ltd | Production of high-purity titanium oxide |
| CN1199385A (en) * | 1996-07-25 | 1998-11-18 | 科尔－麦克基化学有限责任公司 | Method and apparatus for producing titanium dioxide |
| US6350427B1 (en) * | 1999-07-27 | 2002-02-26 | Kerr-Mcgee Chemical Llc | Processes for reacting gaseous reactants containing solid particles |
| US6419893B1 (en) * | 2000-09-18 | 2002-07-16 | Kerr-Mcgee Chemical Llc | Process for producing and cooling titanium dioxide |
-
2007
- 2007-10-09 DE DE102007048553A patent/DE102007048553A1/en not_active Withdrawn
- 2007-11-19 TW TW096143630A patent/TWI422527B/en not_active IP Right Cessation
- 2007-12-11 MX MX2009005234A patent/MX2009005234A/en active IP Right Grant
- 2007-12-11 JP JP2009541828A patent/JP5409379B2/en active Active
- 2007-12-11 EP EP07856539.7A patent/EP2129626B1/en active Active
- 2007-12-11 AU AU2007338499A patent/AU2007338499B2/en active Active
- 2007-12-11 RU RU2009127656/05A patent/RU2440297C2/en not_active IP Right Cessation
- 2007-12-11 WO PCT/EP2007/010780 patent/WO2008077476A2/en active Application Filing
- 2007-12-11 CN CN200780044640.0A patent/CN101547865B/en active Active
- 2007-12-12 SA SA110320025A patent/SA110320025B1/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3532462A (en) * | 1963-04-27 | 1970-10-06 | Bayer Ag | Method of effecting gas-phase reactions |
| US3306760A (en) * | 1964-01-04 | 1967-02-28 | Bayer Ag | Process for carrying out gas phase reactions |
| DE1259851B (en) * | 1965-04-15 | 1968-02-01 | Bayer Ag | Process for the production of inorganic, solid products by gas phase reaction |
| US3725526A (en) * | 1969-08-20 | 1973-04-03 | Montedison Spa | Process for producing pigment quality titanium dioxide |
| US3663283A (en) * | 1969-10-02 | 1972-05-16 | Richard A Hebert | Process and apparatus for the production of finely-divided metal oxides |
| US20020155059A1 (en) * | 2001-04-24 | 2002-10-24 | Tekna Plasma Systems Inc. | Plasma synthesis of titanium dioxide nanopowder and powder doping and surface modification process |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102007048553A1 (en) | 2008-06-26 |
| EP2129626B1 (en) | 2019-01-23 |
| JP5409379B2 (en) | 2014-02-05 |
| CN101547865A (en) | 2009-09-30 |
| AU2007338499A1 (en) | 2008-07-03 |
| WO2008077476A2 (en) | 2008-07-03 |
| SA110320025B1 (en) | 2014-06-25 |
| RU2440297C2 (en) | 2012-01-20 |
| AU2007338499B2 (en) | 2012-11-01 |
| MX2009005234A (en) | 2009-06-05 |
| RU2009127656A (en) | 2011-01-27 |
| JP2010513196A (en) | 2010-04-30 |
| WO2008077476A3 (en) | 2008-11-20 |
| TW200846288A (en) | 2008-12-01 |
| TWI422527B (en) | 2014-01-11 |
| EP2129626A2 (en) | 2009-12-09 |
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